Three-dimensional helical coordination networks of a hexanuclear manganese metallamacrocycle as a helical tecton

Article abstract of DOI:10.1021/ic049393j

We report on helical coordination networks that were prepared using a hexanuclear manganese metallamacrocycle as a helical tecton. We were able to prepare the three-dimensional helical coordination networks using a hexanuclear manganese metallamacrocycle, [Mn₆(lshz)₆], as a helical tecton, where N-lauroyl salicylhydrazide (H₃lshz) was used as the primary building unit to generate the helical tecton as a secondary building unit. While the 4₁/4₃ screw symmetry-linked helical coordination network was obtained when the primary building units had an N-acetyl group, both the 3₁/3₂ screw symmetry-linked and the 4₁/4₃ screw symmetry-linked helical coordination networks were obtained simultaneously in the same batch when the primary building unit had a long alkyl N-lauroyl group at the N-acetyl site.

Full text of DOI:10.1021/ic049393j

Inorg. Chem. 2004, 43, 8230−8232
Three-Dimensional Helical Coordination Networks of a Hexanuclear
Manganese Metallamacrocycle as a Helical Tecton
Dohyun Moon,† Jiheh Song,† Beom Jin Kim,‡ Byoung Jin Suh,‡ and Myoung Soo Lah*,†
Department of Chemistry and Applied Chemistry, College of Science and Technology,
Hanyang UniVersity, Ansan, Kyunggi-Do 426-791, Korea, and Department of Physics,
Catholic UniVersity of Korea, Puchon, Kyunggi-Do 420-473, Korea
Received May 10, 2004
We report on helical coordination networks that were prepared
using a hexanuclear manganese metallamacrocycle as a helical
tecton. We were able to prepare the three-dimensional helical
coordination networks using a hexanuclear manganese metal-
chiral separation, asymmetric catalysis, and nonlinear optic
applications. Organic and/or metallic tectons can be used
3
to generate one-dimensional and two-dimensional helical
4
coordination networks. However, only a few helical tectons
have been utilized for the construction of three-dimensional
lamacrocycle, [Mn
salicylhydrazide (H
generate the helical tecton as a secondary building unit. While
the 4 /4 screw symmetry-linked helical coordination network was
obtained when the primary building units had an N-acetyl group,
both the /3 screw symmetry-linked and the /4 screw
6
6
(lshz) ], as a helical tecton, where N-lauroyl
5
helical coordination networks.
3
lshz) was used as the primary building unit to
Many coordination networks constructed from smaller
molecular units have been reported. However, coordination
networks constructed from nanoscale macrocyclic secondary
building units are less common. There has been a report on
the construction of a three-dimensional coordination network
using a dodecanuclear cadmium metallamacrocycle as the
1
3
3
1
2
4
1
3
symmetry-linked helical coordination networks were obtained
simultaneously in the same batch when the primary building unit
had a long alkyl N-lauroyl group at the N-acetyl site.
6
nanoscale macrocyclic secondary building unit. The met-
allamacrocycle served as a helical tecton, and a bridging exo-
bidentate ligand, 1,2-bis(4-pyridyl)ethene, connected the
1 2
helical tecton via a 3 /3 screw symmetry to form the three-
The rational design of novel coordination networks is of
great interest, because the topology of these networks can
be manipulated to influence the properties and functions of
(
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building units made up of metal ions and organic ligands
for the spontaneous self-assembly of a well-defined structural
entity. The most frequently occurring structural motifs in the
coordination networks are linear or bent ditopic, triangular
tritopic, tetrahedral or square planar tetratopic, and octahedral
2
hexatopic tectons. Various one-dimensional, two-dimen-
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been constructed using these tectons. Among the many
coordination networks known, helical coordination networks
are of particular interest, owing to their potential utility in
9
86. (c) Evans, D. A.; Woerpel, K. A.; Scott, M. J. Angew. Chem.,
Int. Ed. Engl. 1992, 31, 430.
(
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*
To whom correspondence should be addressed. E-mail: mslah@
hanyang.ac.kr.
†
Hanyang University.
Catholic University of Korea.
‡
(
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8230 Inorganic Chemistry, Vol. 43, No. 26, 2004
10.1021/ic049393j CCC: $27.50
© 2004 American Chemical Society
Published on Web 12/02/2004

COMMUNICATION
Scheme 1. Schematic Diagram of the Preparation of the
Three-Dimensional Helical Coordination Networksa
a
The helical tectons, the secondary building units built from H3shz and
metal ions, are linked via exo-bidentate bpea ligand to form two different
tertiary structure three-dimensional helical coordination networks. The three-
dimensional helical coordination networks were obtained by substitution
of the coordinated solvent molecules of the hexanuclear manganese
metallamacrocycle using a bpea.
dimensional helical coordination network. We have also
demonstrated the construction of a three-dimensional helical
coordination network using a hexanuclear manganese met-
7
allamacrocycle as the helical tecton. A new type of metal
cluster, a hexanuclear manganese metallamacrocycle, was
prepared as a helical tecton using the pentadentate ligand,
N-acetyl salicylhydrazide (H ashz), and manganese ions as
3
Figure 1. Diagrams of the [Mn6(lshz)6(DMF)2(bpea)2] network, 1. (a) A
line drawing diagram showing that most of the channel cavities are filled
with long alkyl groups. (b) A schematic diagram. Key: red ) metallamac-
rocycle and DMF; blue ) bpea.
the primary building units. In this three-dimensional coor-
dination network, the hexanuclear manganese metallamac-
rocycle served as a helical tecton, and 1,2-bis(4-pyridyl)-
The crystals with a rectangular morphology had an
isostructural helical coordination network architecture, the
9
ethane (bpea) connected the helical tecton via a 4
1
/4
3
screw
same as those with H ashz. The potential pentadentate
3
symmetry. The coordination network contains three-dimen-
sional solvent channels, in which the N-acetyl side chains
are exposed to the channel.
ligand, H lshz, connected the metal ions via diaza linkages,
as shown in Scheme 1, to construct the hexanuclear
manganese metallamacrocycle as a secondary building unit.
3
The three-dimensional coordination network, [Mn
DMF) (bpea) ] (1), was obtained by substitution of the
alternating coordinated solvent molecules of the hexanuclear
manganese metallamacrocycle, [Mn (lshz) (DMF) ], using
a bridging exo-bidentate ligand, bpea. The hexanuclear
manganese metallamacrocycle acting as a helical tecton was
6 6
(lshz) -
In this study, we have introduced the lauroyl group at the
N-acetyl group site of the primary building units to modify
the hexanuclear manganese metallamacrocycle with a reten-
tion of the helical tectonic feature. We have observed the
effect of the long alkyl side chain on the formation of the
helical coordination network. In contrast to the construction
of a three-dimensional helical coordination network using
(
2
2
6
6
6
connected through the bpea linkers via a 4
symmetry, in which the long alkyl side chains of the lshz
ligands were packed in the solvent channels observed in the
[Mn (ashz) (DMF) (bpea) ] network, leaving only 16 isolated
1 3
/4 screw
3-
H
3
ashz as the primary building unit, a similar preparation
using N-lauroyl salicylhydrazide (H lshz) resulted in two
different forms of crystals occurring in the same batch
Scheme 1).
3
8
6
6
2
2
DMF solvent sites per unit cell (Figure 1).
The crystals with rhomboidal morphology had the same
helical tecton, but had a completely different helical coor-
(
(
(
7) Moon, M.; Kim, I.; Lah, M. S. Inorg. Chem. 2000, 39, 2710-2711.
8) [Mn6(lshz)6(bpea)2(DMF)2], 1, and [Mn6(lshz)6(bpea)2(DMF)2]3‚[Mn6-
(
lshz)6(DMF)6], 2: A 0.167 g (0.499 mmol) sample of H3lshz was
(9) Crystal data for [Mn6(lshz)6(DMF)2(bpea)2], 1: 0.85 × 0.55 × 0.35
3
dissolved in 15 mL of DMF. A 0.046 g (0.250 mmol) sample of bpea
was then added to the solution, which was stirred for 5 min. When all
the ligands were completely dissolved, a 0.123 g (0.502 mmol) sample
of manganese(II) acetate tetrahydrate was added to the solution,
without the solution being stirred. The solution was allowed to stand
for a week, whereupon a mixture of rectangular and rhombic-shaped
dark brown crystals was obtained, 0.217 g, 91% total yield for the
mixture. Anal. Calcd for [Mn6(lshz)6(bpea)2(DMF)2]‚0.5(DMF), 1
mm , dark brown crystals, tetragonal, I41/a, a ) b ) 41.4326(5) Å,
3
c ) 17.75560(10) Å; V ) 30480.3(5) Å , Z ) 16, Fcalcd ) 1.298 g
-
1
-1
cm , µ(Mo KR) ) 0.553 mm , 2θmax ) 48.5°. R1 ) 0.0490 for
10772 reflections of I > 2σ(I), R1 ) 0.0573, wR2 ) 0.1393 for all
12174 reflections. The largest difference peak and hole were 0.574
-
3
and -0.380 e‚Å , respectively. Crystal data for [Mn6(lshz)6(bpea)2-
3
(DMF)2]3‚[Mn6(lshz)6(DMF)6], 2: 0.48 × 0.48 × 0.40 mm , dark
brown crystals, hexagonal, R 3h , a ) b ) 51.668(5) Å, c ) 20.345(3)
3
-1
(
9
C145.5H207.5N18.5O22.5Mn6) (fw ) 2869.46): C, 60.90; H, 7.15; N,
Å; V ) 47035(10) Å , Z ) 18, Fcalcd ) 1.192 g cm , µ(Mo KR) )
-1
.03%. Found for 1: C, 61.06; H, 6.86; N, 9.33%. Anal. Calcd for
0.533 mm , 2θmax ) 50°. R1 ) 0.0818 for 8763 reflections of I >
2σ(I), R1 ) 0.1401, wR2 ) 0.2540 for all 18449 reflections. The
[
Mn6(lshz)6(bpea)2(DMF)2]3‚[Mn6(lshz)6(DMF)6]‚9(H2O)‚7(DMF), 2
-
3
(C585H871N79O100Mn24) (fw ) 11929.33): C, 58.90; H, 7.36; N, 9.28%.
largest difference peak and hole were 0.804 and -0.461 e‚Å
Found for 2: C, 58.70; H, 7.47; N, 9.26%.
respectively.
Inorganic Chemistry, Vol. 43, No. 26, 2004 8231

COMMUNICATION
)
4.29%) per Mn24 unit, respectively. The remaining
multistage additional 50+% weight losses occur at T > 210
C.
The crystals of network 1 are diffracting, even after heating
°
the crystals to 180 °C. The crystals of network 2 are also
diffracting after drying in air for 1 day. However, these
crystals are only weakly diffracting after heating to 180 °C.
When both sets of crystals were soaked in various solvents,
including DMF and chloroform, they lost their crystallinity,
so that it was not possible to check the guest binding inside
the channels for these solvents. However, the reintroduction
of DMF solvent in the dried crystals of network 2 via vapor
diffusion showed a partial recovery of the diffraction
intensities.
The magnetic behavior of both networks is very sim-
ilar to that of the nonconnected hexanuclear manganese
metallamacrocycle, [Mn
and the effective magnetic moment, µeff ) 4.9(1) µ
6
(lshz)
6
(DMF)
6
] (J ) -2.53(3) K,
, per
B
manganese center (unpublished)). The characteristic magnetic
behavior of these networks is antiferromagnetic couplings.
The best fit of the data of each network using a Curie-
Weiss law gives rise to the exchange parameters between
the neighboring centers of J ) -3.06(3) and -2.93(3) K,
and an effective magnetic moment of µeff ) 4.9(1) and 5.0-
Figure 2. Diagrams of the [Mn6(lshz)6(bpea)2]3‚[Mn6(lshz)6(DMF)6]
network, 2. (a) A line drawing diagram. (b) A schematic diagram. The one-
dimensional channels run parallel to the crystallographic c-axis and the
nonconnected metallamacrocycles are packed in the channels. Key: red )
metallamacrocycle; blue ) bpea; green ) nonconnected metallamacrocycle.
(1) µ
B
per manganese center for networks 1 and 2, respec-
tively.
dination network architecture, [Mn
6
(lshz)
], 2. The hexanuclear manganese metallamac-
(lshz) ], in the rhomboidal crystal structure,
6
(bpea)
2
]
3
‚[Mn
6
-
In conclusion, we have constructed a helical coordination
network with a hexanuclear manganese metallamacrocycle
as a helical tecton. While a 4 /4 screw symmetry-linked
1 3
helical coordination network was obtained as the sole product
when the primary building unit had an N-acetyl group, both
9
6 6
(lshz) (DMF)
rocycle, [Mn
6
6
retains the helical tectonic feature observed in the metal-
lamacrocycle, of the helical coordination in network 1 of
the rectangular crystal structure. The helical tecton with a
1 2 1 3
a 3 /3 screw symmetry-linked and a 4 /4 screw symmetry-
6
noncrystallographic local pseudo-S symmetry was in the
linked helical coordination network were obtained simulta-
neously in the same batch when the primary building unit
had a long alkyl N-lauroyl group at the N-acetyl site.11
Modification of the metallamacrocycle with retention of the
helical tectonic feature resulted in a different coordination
network architecture, but the helicity of the coordination
network was preserved in a different mode.
crystallographic inversion center. As in network 1, four of
the six solvent sites in the building unit were exchanged with
bpea. However, the helical tectons were networked in a
different fashion, via a 3 /3 screw symmetry (Figure 2). This
1 2
helical network architecture leads to the formation of large,
one-dimensional channels of around 2.0 nm in diameter. The
hexagonal channels running along the S
parallel to the crystallographic c-axis and are occupied by
unconnected [Mn (lshz) (DMF) ] hexanuclear manganese
metallamacrocycles.
6
symmetry sites are
Acknowledgment. We wish to thank the Korean Institute
of Basic Science for carrying out the elemental analyses.
The authors wish to acknowledge the financial support of
KISTEP (M1-0213-03-0004) and CBMH.
6
6
6
Thermogravimetric analysis (TGA) data for network 1
carried out in flowing nitrogen gas indicates a two-stage
weight loss. The first weight loss of 1.3% occurs up to 180
Supporting Information Available: X-ray crystallographic file
in CIF format and TGA data for 1 and 2, and magnetic data in the
temperature range 2-300 K for [Mn (lshz) (DMF) ], 1 and 2. This
6 6 6
°
C, and corresponds to the loss of half of the DMF molecules
per Mn
unit (calcd ) 1.27%).10 The second weight loss of
around 80% from 250 to 400 °C is associated with the MnO
6
2
material is available free of charge via the Internet at http://
framework. The TGA data for network 2 show multistage
pubs.acs.org.
weight losses. The first loss of 1.4% at temperatures up to
IC049393J
7
0 °C and the second weight loss of an additional 4.2% up
to 190 °C correspond to the loss of nine water molecules
calcd ) 1.36%), and the loss of seven DMF molecules (calc.
(
(11) When the long lauroyl group was introduced as a side chain, the solvent
channels that formed from the architecture of network 1 could barely
accommodate the long alkyl side chains that may make the stability
of network 1 comparable to that of network 2.
(10) The elemental analysis data are in conformity with TGA results.
8232 Inorganic Chemistry, Vol. 43, No. 26, 2004